Journal of Environmental Chemical Engineering 5 (2017) 5381–5388

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Journal of Environmental Chemical Engineering

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Adsorption of distillery spent wash on activated bagasse fly ash: Kinetics and T

thermodynamics
⁎
Jemal Fitoa, , Nurelegne Teferab, Stijn W.H. Van Hullec
a
Ethiopian Institute of Water Resources, Addis Ababa University, P.O. Box 150461, Addis Ababa, Ethiopia
b
Addis Ababa Science and Technology University, Ethiopia
c
Department of Industrial Biological Sciences, Ghent University, Graaf Karel de Goedelaan 5, B-8500, Kortrijk, Belgium

A R T I C L E I N F O A B S T R A C T

Keywords: This study aimed to characterize distillery spent wash and COD removal from it using bagasse fly ash (BFA). The
Adsorption results of the analyses showed that the average value of BOD5 and COD were 35,990 mgL−1 and 13,9671
Bagasse fly ash mgL−1, respectively. High amount of total nitrogen (1217 mgL−1), total phosphorous (45 mgL−1), total solids
COD removal (156 mgL−1) and low acidity (pH 4) were recorded. Adsorption of this spent wash on BFA was investigated at
Kinetics
different temperatures, contact times, initial COD concentrations, pH solutions and adsorbent (BFA) doses.
Spent wash
Raising temperature from 15 to 328 K resulted in increasing the uptake of the organic matter from 29.5 to
Thermodynamics
75.5%. Varying the initial COD concentration from 1000 mgL−1 to 6000 mgL−1 increased the adsorptivity
capacity (qe) from 6 to 92.40 mg g−1 and resulted in an increase in removal efficiency from 24 to 61.6%.
Adsorptive capacity (116.30 mg g−1) calculated by the pseudo-second order model (R2 = 0.98) indicated that
pseudo-second order kinetic model fitted better with the experimental data. Moreover, the Gibbs free energy
change (ΔG) (−5.61 to −11.84 kJ mol−1)) showed that adsorption process was spontaneous whereas the po-
sitive value of the ΔH (42.29 kJ mol−1) indicates an endothermic process. Similarly, increasing the degree of
disorder at the liquid-solids interfaces was observed from entropy change (ΔS = 0.17 kJ (Kmol)−1). In general,
thermodynamic study revealed that adsorption process was feasible, spontaneous and endothermic; and the
application of BFA is the promising option for removal of organic matter (COD) from molasses spent wash.

1. Introduction
The rapid advancement of industrialization and progress of civili-
zation has drawn special attention to the improper handling of waste
materials that resulted in environmental degradation [1]. Today, our
environment is continuously degrading due to the disposal of industrial
wastes into the ambient environment [2]. Hence, industrial pollution is
a major factor that causes the degradation of the environment which is
affecting the water consumed, the air inhaled and the soil lived on [3].
Industrial waste management is one of the most important environ-
mental problems faced by today’s world because industrial processes
create a variety of wastewater pollutants that are difficult to handle and
expensive to treat [4]. Furthermore, the demand for water and the
generation of wastewater is increasing at an alarming rate while the
disposal of wastewater is still a major problem faced by many industries
due to the complexity and huge volume of effluent with very limited
space for treatment and disposal [5].
Alcohol distilleries are extensively growing because of the varia-
bility of oil prices and the consumption of ethanol as the energy source
and raw material for many industries [6]. The unique nature of alcohol
distilleries is the consumption of high volume of raw water. However,
the majority of the input materials end up in the form of wastes [7]. The
distillery wastes account 88% to 95% of total volume whereas the
ethanol contains only 5% to 12% of the raw materials [8]. In line with
this, for every liter of ethanol production, about 12 to 15 L of distillery
spent wash is generated [9]. Indeed, ethanol distillery is one of the
major agro-based industries which generate spent wash as the residue
of fermented mash. Usually, the term vinasse or molasses spent wash is
commonly used for distillery wastewater. During ethanol production in
the fermentation process, diluted molasses is used with supplements
such as yeast, ammonium sulphate, urea and phosphate while the ad-
justment of pH for fermentation broth is made by sulphuric acid [6].
These supplements are the major contributor to spent wash pollution.
Distillery spent wash properties described in terms of a recalcitrant,
complex, high organic matters of COD (80,000 to 160,000 mgL−1), low
acidity (pH 3.7 to 4.5) with high content of dissolved inorganic salts
[10]. The dark brown color of the spent wash is due to the presence of
the color causing pigment known as melanoidins (C17–18H26–27O10N)

⁎
Corresponding author.
E-mail address: fitojemal120@gmail.com (J. Fito).

http://dx.doi.org/10.1016/j.jece.2017.10.009
Received 12 August 2017; Received in revised form 30 September 2017; Accepted 2 October 2017
Available online 07 October 2017
2213-3437/ © 2017 Elsevier Ltd. All rights reserved.
J. Fito et al.
which is formed under non-enzymatic (Maillard) reaction between
sugar and amino compounds at high temperature[11].The peculiar
feature of melanoidins are very acidic, long polymeric and highly dis-
persed colloidal particles with the negatively charged surface due to the
dissociation of carboxylic acids and phenolic groups [12]. Phenols,
melanin and caramels are others color causing compounds. The pre-
sence of these recalcitrant components in the spent wash makes it
hardly degradable in the different (biological) wastewater treatment
stages and results in the discharge into the environment [6]. As dis-
tillery spent wash is an eco-toxic effluent that is unsafe to dispose into
agricultural and aquatic ecosystem [13], ethanol distilleries are con-
sidered as a major polluting industry. In India, for example, distilleries
are grouped under the “Red Category” by the Central Pollution Control
Board due to the severity of the pollution caused by the spent wash
[10].The acidity of the spent wash enhances the dissolution of metals in
the water bodies whereas the dark brown color of spent wash hinders
photosynthesis activities by blocking sunlight [14]. Additionally, direct
discharging of untreated effluent into the water bodies might be lead to
eutrophication [15].
Cost-effective and efficient treatment methods for distillery spent
wash are still under investigation but the pollution controlling gov-
ernment policies are more and more stringent. Conventional waste-
water treatment systems usually consist of primary treatment to remove
solids, oils and fats; secondary biological treatment to remove organic
matter and nutrients and tertiary treatment such as polishing stage
[16]. Various conventional physicochemical methods such as coagula-
tion– flocculation, filtration and different combinations of these
methods have also been tested for the treatment of distillery spent
wash, but were not effective. Furthermore, the conventional biological
treatments such as trickling filter and activated sludge are better but
inefficient in the removal of the color causing pigments, the dark brown
color. Among the current treatment technologies, high rate anaerobic
treatment is the most suitable and attractive primary treatment option
for high strength organic effluents such as distillery spent wash [17].
However, the color causing pigments of spent wash are not effectively
degraded by primary biological treatment because only about 6–7% of
pollutants are removed by conventional biological methods [18]. This
showed that anaerobic treatment alone cannot remove organic and
inorganic pollutants to permissible discharging limits. Hence, other
treatment methods like adsorption can be coupled with the biological
method in removing color causing pigment and organic matter (COD)
by low-cost adsorbents which have also the advantage of simulta-
neously removing of other inorganic pollutants such as nutrients, salts
and metals.
Adsorption is more popular among many treatment methods be-
cause of its simple design, easy operation and the possibility of ad-
sorbent re-use or recycling. This technology is commonly employing in
wastewater treatment because of its economic viability, technical fea-
sibility and socially acceptability [19]. Today, special attention is given
for agro-based inexpensive adsorbents such as sugarcane bagasse, wood
sawdust, bagasse fly ash, wood ash and rice husk because of their
minimum environmental polluting effect [20]. The application of such
adsorbents for the treatment of wastewater is increasing rapidly due to
the growth of awareness of public and environmental protections [21].
Usually, adsorption technique is attractive if the adsorbent material
used is cheap, more efficient, available and does not require any ex-
pensive pretreatment process.
The development of adsorbent from industrial by-products like ba-
gasse fly ash (BFA) is a potential research area because of the com-
mercially activated carbon is expensive. BFA is by-product from the
powerhouse of the sugar factory. The application of this adsorbent for
the wastewater treatment is proved to be an effective and attractive
process. For instance, 78% removal efficiency was achieved through
adsorption of acrylonitrile on BFA from the aqueous solution of
100 mgL−1 [22]. BFA adsorptive capacity of 101.5 mg g−1 was also
reported for the treatment of dairy wastewater (COD 3900 mgL−1)
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Journal of Environmental Chemical Engineering 5 (2017) 5381–5388
[23]. In another study, in the removal of malachite green dye from
aqueous solution with BFA, commercially graded and laboratory made
activated carbons, BFA showed a wide pore size distribution with the
good surface area which helps to interact with the different size of
adsorbates in the treatment process [24]. Moreover, BFA has good
porous structure and adsorption capacity, in addition to, easily mod-
ified nature by chemical treatment to increase its adsorptive properties.
In sorption behaviors comparison of BFA with commercially activated
carbon, the BET surface area, bulk density and heating value of acti-
vated carbons commercial were 336.6 m2g−1, 599.32 kgm−3 and
18.81 MJkg−1 whereas these properties for BFA were 168.39 m2g−1,
185.51 kgm−3 and 19.23 MJkg−1, respectively [23]. Hence, BFA has a
potential to substitute commercially available carbon due to its com-
parable efficiency and a significantly low-cost [25]. The application of
BFA for the treatment of industrial dye wastewater resulted in removal
of COD (51%), color (70%), turbidity (71%) and TSS (96%) [26]. Si-
milarly, the treatment of synthetic dairy wastewater by means of ad-
sorption onto the activated carbon-commercial and BFA resulted in a
maximum COD removal of 68.7% and 26%, respectively [23].
However, adsorption technology using activated carbon like BFA
has some restrictions such as the cost of the activated carbon, the need
for regeneration after exhausting and the loss of adsorption efficiency
[27]. Practically, some adsorbents are disposed of without the re-
generation because of their low cost and unlimited availability. Re-
generation of BFA usually carried out many times throughout the
treatment process either by thermal or solvent desorption. For instance,
solvents such as aqueous solution (usually about 0.1 N) of HCl, H2SO4,
HNO3, CH3COOH, C2H5OH, acetone NaOH and distilled water are very
effective and commonly used in regeneration processes [28].
Disposal of BFA as solid waste to the environment causes a huge
problem in sugar industries particularly at Metahara sugar factory. The
attempt of employing of this by- product as an adsorbent for wastewater
treatment is the good solution for the environment and wonderful
practice of waste to resources conversion. Many kinds of research
conducted so far on adsorption treatment of organic matter removal
from wastewater have been focused on either to investigate the effi-
ciency of the treatment or the equilibrium isotherms. However, in this
study, adsorption kinetics and thermodynamics are investigated during
removal of organic matter from distillery spent wash. Therefore, the
intention of this study is to assess the physicochemical properties of the
distillery spent wash and its treatment with activated BFA.
2. Materials and methods
2.1. Adsorbent
2.1.1. Adsorbent development
Bagasse fly ash was collected from the dumping site of the Metahara
sugar factory in the regional state of Oromiya (Ethiopia). It was taken to
laboratory and sun-dried for two days. For organic matter removal from
the surface of adsorbent, it was soaked in hydrogen peroxide (30% by
concentration) at 60 °C for 24 h. Then it was washed with de-ionized
water repeatedly until all hydrogen peroxide on the surface was re-
moved. This activated bagasse fly ash (BFA) was placed into an oven at
100 °C until it was dried completely. Finally, it was powdered, sieved
and stored in a vacuum desiccator until it was used for the treatment
[29].
2.1.2. Adsorbent characterization
A surface morphology of adsorbent (BFA) was determined using the
scanning electron microscope and SEI resolution 1.0 nm guaranteed at
15 kV (JEOL JSM-7600F FEG-SEM, JEOL, USA). The sample was ap-
plied on carbon tape, and measured at a working distance of 8 mm. The
sample preparation and analysis was done as per the standard operating
procedure of JEOL JSM 7600F SEM which was operated at 15 kV and
current of 10 A under 1000× magnifications [19].
J. Fito et al.
2.2. The effect of initial COD concentration on adsorption
Wastewater samples were taken in bottles with glass-stoppered and
tests were performed without delay on the same day. The most popular
current testing method for COD is open reflux method which is suitable
for a wide range of wastes such as distillery spent wash. A wastewater
sample was refluxed in strongly acid solution with a known excess of
potassium dichromate (K2Cr2O7). After digestion, the remaining un-
reduced K2Cr2O7 is titrated with ferrous ammonium sulphate to de-
termine the amount of K2Cr2O7 consumed and the oxidizeable matter
was calculated in terms of oxygen equivalent. Due to it is higher oxi-
dizing ability dichromate reflux method was preferred over other pro-
cedures using other oxidants. Hence, the COD concentration of waste-
water was determined by open reflux method (APHA 5220 B) and
dilution process was performed by distilled water at laboratory scale
[30]. The effect of initial COD concentration on treatment efficiency
was investigated at a constant adsorbent dose (4 g in 100 mL solution),
pH (8), and the contact time of the treatment (4 h) under various initial
COD concentrations such as 1000, 2000, 3000, 4000, 5000 and 6000
mgL−1.
2.3. The effect of pH on adsorption
The effect of pH on removal efficiency of organic matter on bagasse
fly ash form distillery spent was tested at screening stage of the treat-
ment. The pH range of 3–8 was selected and its effects on adsorption
were recorded under the experimental condition of COD concentration
6000 mgL−1, adsorbent dose 4 g in 100 mL solution, contact time 4 h
and temperature of 25°C.
2.4. Adsorption kinetics
Batch adsorption kinetics tests were carried out using different
contact time under fixed experiment condition (Table 1). Wastewater
samples were taken and placed into 250 mL conical flasks; and agitated
at 160 rpm using water bath shaker at the fixed temperature of 25 °C.
Afterwards, the solution was centrifuged at 3500 rpm for 30 min. Fi-
nally, the solution was filtered using Whatman filter paper 42 and the
COD analysis was performed as per standard methods for the ex-
amination of water and wastewater [30].
The amounts of organic matter adsorbed onto activated carbon was
determined according to Eq. (1).
c0 −ct
qt = v (G7126, Sigma-Aldrich) and 0.42 g of sodium bicarbonate in 100 mL of
m (1)
where co is initial concentration of COD and ct is concentration of COD
at contact time of t whereas v is the volume of the adsorbate and m is
the mass of the adsorbent in g. Similarly, qe can be calculated as the
amount of organic matter adsorbed onto activated carbon at equili-
brium.
2.5. Adsorption thermodynamics
Batch experimental adsorption thermodynamics was performed in
Table 1
Adsorption kinetics conditions and adsorbent (BFA) particle size.
Contact time(h) COD mgL−1 pH Adsorbent (g) Temp. (°C)
1 6000 8 4 25
2 ammonia, nitrate, total nitrogen, phosphate, total phosphorus and
3 sulphates. These analyses were carried out for four solid months and the
4
5
6 The average values of temperature 47.66 °C and pH 4.01 were re-
where APS is adsorbent (BFA) particle size.
Journal of Environmental Chemical Engineering 5 (2017) 5381–5388
250 mL conical flasks. Wastewater samples were agitated at 160 rpm
using water bath shaker which was operated at the predetermined
different temperatures indicated in Table 2. Then the agitated samples
were centrifuged and filtered through Whatman filter paper 42. Finally,
the filtrate samples were tested for a change in COD concentration and
the amount of organic matter adsorbed was calculated according to Eq.
(1).
2.6. Spent wash collection
Ethanol distillery spent wash samples were collected from Metahara
sugar and distillery factory located in Oromiya regional state, Ethiopia.
The wastewater samples were taken at the discharge point of the fac-
tory in plastic bottles that were pre-cleaned with acid. After the sam-
pling, the effluent samples were immediately taken to the laboratory
and stored in the refrigerator at 4 °C until they were used for analyses.
The frequency of sampling was done on the monthly based interval,
four times throughout the study period. Composite sampling techniques
were applied for physicochemical analyses which measured in the la-
boratory and grab sampling techniques were used for physical para-
meters that analyzed onsite at sampling points.
2.7. Physicochemical analyses
Temperature, pH and electrical conductivity (EC) were measured
immediately on sites while other the physico-chemical parameters such
as total solids (APHA 2540 B, Total solid dried at 103–105 °C), am-
monia (APHA 4500, MgO Distillation methods), nitrate (APHA 4500-
NO3− B, Ultraviolet spectrophotometric screening methods), total ni-
trogen (APHA 4500B, B- Kjldahal Test), phosphate (APHA 4500-P-
C,Vandomolybdophosphoric acid), total phosphorus (APHA 3030F and
APHA 4500-P), chemical oxygen demand (APHA 5220 B, Open reflex
method), biochemical oxygen demand (APHA 5210 B, 5-days BOD
test), chloride (APHA 4500-Cl-B, argentometric) and sulphate (APHA
3030E, turbidmetric method) were measured in the laboratory as per
standard methods for the examination of water and wastewater [30].
2.8. Preparation of synthetic wastewater
Melanoidins is a constituent of distillery spent wash. To minimize
the interferences from distillery spent wash with adsorption treatment,
melanoidins containing distillery wastewater was prepared by mixing
4.5 g of glucose (G8270 D-(+), Sigma-Aldrich), 1.88 g of glycine
distilled water which was heated for 7 h at 95°C until dried. Then
100 mL of distilled water was added to form a melanoidins solution
[31]. Finally, dilution of wastewater solution was made accordingly
and the pH adjustment was performed using 0.1 M NaOH and 0.1 M
HCl solutions. The COD of the synthetic wastewater was determined as
per the standard methods for the examination of water and wastewater
[30] and its treatment was performed with activated carbon (BFA) at
different concentrations.
3. Results and discussion
3.1. Physicochemical properties of distillery spent wash
The physicochemical properties of spent wash were investigated
APS
and the results of analyses were described in terms of total solids (TS),
< 162 μm temperature, pH, electrical conductivity (EC), chloride, BOD, COD,
results are presented in Table 3.
corded in raw spent wash which are out of the Ethiopian distillery ef-
fluent discharging limits 40 °C and 6 to 9, respectively. The increase in
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Table 2
Thermodynamic conditions for adsorption process.

Temperature (°C) COD mgL−1 pH Adsorbent dose Contact time Centrifugation

15 6000 8 4g 4h 350 rpm (30 min)

25
35
45
55

effluent temperature has a great impact on the environment by accel-
erating chemical reactions and rate of biological process in water body
and soil that received the effluent. In such conditions, it would be a
great threat to the survival of various biological communities. The
acidic nature of distillery effluent may be attributed to the amount of
sulphuric acid that is consumed for pH adjustment in broth fermenta-
tion. Moreover, acidity is one of the essential biotic factors that can
serve as pollution index and also influence the rate of biological reac-
tion which determines the survival of various microorganisms [3].
The distillery spent wash organic matter COD and BOD found to be
139671 mgL−1and 35989 mgL−1, respectively. These values are ex-
tremely exceeding the recommended level set by Ethiopian distillery
effluent discharging limits which are COD 250 mgL−1and BOD5
60 mgL−1. The disposal of effluent with such high loads of BOD and
COD into the stream and land can create toxic conditions by immediate
depletion of oxygen which disturbs the water chemistry and biological
communities. Both total nitrogen (1217 mgL−1) and total phosphorous
(45 mgL−1) contents were exceeding the discharging limits which are
40 mgL−1and 5 mgL−1, respectively. Probably, the presence of these
pollutants is caused by the nitrogen and phosphorous sources that are
added during the fermentation process. The unique thing about this
distillery effluent analysis is the value of ammonia (14.04 mgL−1)
which was within the range of recommended level (20 mgL−1).
Additionally, the nitrate (4.06 mgL−1) and phosphate (20.99 mgL−1)
were also obtained. Urea (CO (NH2)2) is used as a nitrogen-release
fertilizer and source of nutrient for yeast (saccharomyces cerevisiae) for
bioethanol production. Furthermore, diammonium phosphate (DAP)
((NH4)2HPO4) fertilizer is an excellent source of P and nitrogen (N)
which is commonly used in distillery fermentation. Metahara ethanol
distillery data indicated that urea and DAP fertilizers are applied at the
rate of 1.81 and 0.63 kg(kL)−1 of ethanol, respectively. These condi-
tions might be attributed to high concentrations of nitrogen and
phosphorus sources of distillery spent wash. Thus, the pollutants are
potential contributors for eutrophication of lakes, rivers and another
water bodies which received the effluent.
High amount of total solids 156 gL−1 was recorded which also
extremely exceeded the discharging limits (50 mgL−1). This high
amount of total solid might be due to the insoluble organic and in-
organic matter present in the effluent. When the effluent discharged
into a stream or any water bodies, the enormous total solid particulates
affect the light intensity of water bodies that interfere the natural
aquatic ecosystem. Additionally, the result of other parameters such as
electrical conductivity (43.6 mScm−1), chloride (6476 mgL−1) and
sulphates (4983 mgL−1) were recorded but there are no standards for
these parameters to monitor the distillery spent wash. These are an-
other pollutants that can cause water and soil pollution with adverse
effects towards the environment.
3.2. The ratio of BOD5 to COD in distillery spent wash
The ratio of BOD5 to COD is a good indicator for the degree of de-
gradability of organic matter by the microbial community and the
nature of biochemical reaction in wastewater treatment plant. Thus, the
correlation between BOD5 and COD in distillery spent wash was in-
vestigated and the results were presented in Table 3. This relation be-
tween BOD5 to COD was positive and linear with a well-defined pattern
was observed. The concept of bio-degradability capacity which is
commonly termed as biodegradability index (BI), is used to provide
basic information for selection of appropriate treatment technology and
treatment plant design. Usually, for fairly degradable and effective
biological treatment, the BOD/COD > 0.6 is expected and for the value
of BI in between 0.3 and 0.6, seeding of acclimatized microorganisms is
required. For BOD/COD < 0.3 biologically treatment becomes difficult
since biodegradation will not proceed [32]. Because of recalcitrant and
refractory compounds in distillery spent wash, sometimes very low
BOD/COD (0.049) was reported which confirmed that very poor bio-
degradability of effluent [33]. In this study, the calculated value of BI in
distillery spent wash was about 0.3 which indicated that biological
treatment is possible but could become difficult. However, the actual
value of BI from the experimental value is 0.26. This is clearly indicated
that another treatment technology has to seek for and the reason why
effective treatment option for distillery spent wash still under

Table 3
Physico-chemical characteristics of distillery spent wash.

Parameters M1 M2 M3 M4 Average ES

pH 3.94 + 0.02 3.96 ± 0.02 3.96 ± 0.09 4.17 ± 0.057 4.01 6–9
EC (mS/cm) 40.3 + 0.42 42.8 ± 0.6 40.7 ± 1.56 50.5 ± 1.02 43.6 –
Temp ((°C) 46.7 + 0.71 47.3 ± 0.25 49.6 ± 0.78 47.2 ± 0.50 47.7 40
TS (g/L) 143.1 + 4.13 157.6 ± 3.71 155.7 ± 3.89 169.4 ± 0.85 156.4 50
BOD(mgL−1) 37661 + 53.74 42880 ± 40.5 35751 ± 55.15 27661 ± 86.97 35990 60
COD (mgL−1) 126684 + 24.25 138207 ± 207 167479 ± 77.78 126316 ± 446.2 139671 250
BOD/COD 0.29 0.31 0.21 0.22 0.26 –
NeNO3− (mgL−1) 2.40 + 0.28 4.03 ± 0.22 5.72 ± 0.820 4.11 ± 0.23 4.06 –
NeNH3 (mgL−1) 12.7 + 0.85 14.21 ± 0.29 17.62 ± 0.57 11.62 ± 0.59 14.04 20
TN (mgL−1) 1151 + 71.82 1355 ± 25.56 1208 ± 42.61 1154 ± 55.85 1217 40
TP (mgL−1) 32.2 + 0.87 41.3 ± 1.09 36.5 ± 1.15 70.8 ± 3.59 45 5
PO43− (mgL−1) 18.97 + 0.62 23.35 ± 0.95 25.515 ± 2.14 16.12 ± 1.39 21.99 –
Cl− (mgL−1) 5968 + 62.15 4862 ± 65.18 7475 ± 120.21 76001 ± 34.14 6476 –
SO4−2 (mgL−1) 4443 + 18.29 4561 ± 7.55 4917 ± 37.47 6012 ± 38.53 4983 –

where M1, M2, M3 and M4 are first, second, third and fourth month of sampling, respectively. But ES refers Ethiopian standard for the maximum permissible limit of distillery spent wash
to be discharged. Each value of the parameter described as mean value ± standard deviation at n = 3.

5384
J. Fito et al.
investigation.
3.3. Bagasse fly ash characterization using scanning electron microscopy
The adsorbent (BFA) surface morphology was investigated using
scanning electron microscopy (SEM) before and after the adsorption
treatment with wastewater. The SEM images of the adsorbent (Fig. 1)
shows that a large number of various size of pores with irregular and
heterogeneous shapes were observed which contributed to the surface
area of adsorbent. This remarkably rough and pores containing surface
revealed that the material is providing the binding sites for adsorbates.
Moreover, the adsorbent morphology after treatment indicated that
significant adsorbent surface change and with diminishing in porosity
was observed due to the interactions between adsorbate and adsorbent.
3.4. The effect of initial COD concentration on adsorption
In this analysis, adsorbent dose (4 g in 100 mL solution), pH (8), and
contact time (4 h) were kept constant but different initial COD con-
centrations such as 1000, 2000, 3000, 4000, 5000 and 6000 mgL−1
were taken. The temperature of the treatment system was monitored in
water bath shaker at the fixed temperature of 25 °C. Adsorption effi-
ciency increases with increasing initial COD concentration due to the
fact that resistant to the uptake of the adsorbate was minimized in such
conditions. The adsorptive capacity (qe) was increased from 6 to
92.4 mg g−1 as the removal efficiency was raised from 24 to 61.6% for
1000 mgL−1 and 6000 mgL−1 initial COD concentration, respectively.
The increase in an initial concentration of adsorbate is due to an in-
crease in driving force of concentration gradient which increases the
mass transfer rate [34]. In another study, the application of bagasse fly
ash as an adsorbent for the removal of brilliant green dye from aqueous
solution resulted in the adsorptive capacity of 65.8 mg g−1 [35]. The
color removal from ink wastewater by sawdust fly ash (85.5 mg g−1),
activated carbon (40.5 mg g−1) and bagasse fly ash (7.3 mg g−1) were
reported [36]. Furthermore, 90% removal of cadmium 14 mgL−1 and
nickel 12 mgL−1 of wastewater was also achieved using BFA [29].
3.5. The effect of pH on adsorption
A screening experiment was conducted to understand the effect of
the pH variations on COD removal efficiency. However, an insignificant
change was observed as the pH values changed from acid media to
alkaline. For instance, the removal percentage of COD was increased by
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Journal of Environmental Chemical Engineering 5 (2017) 5381–5388
Fig. 1. SEM surface of BFA before (left) and after (right) the
treatment with wastewater.
only 9.2% when pH value shifted from 3 to 8 under the experimental
condition of an adsorbent dose of 4 g in 100 mL, contact time 4 h and
initial COD concentration 6 000 mgL−1. This might be attributed to the
effect of the activating agent (hydrogen peroxide) of adsorbent which
enhance the positive valence on the surface on the adsorbent and favors
adsorption phenomena at acidic media for negatively charged spent
wash. Moreover, the adsorptive capacity of BFA was influenced mainly
by the interaction between the adsorbent (BFA), spent wash and the
solution media either the H+ or OH−.
3.6. Adsorption of kinetics study
Batch adsorption experiment was carried out to investigate the ef-
fect of contact time on adsorption process at various time 60, 120, 180,
240 and 300 min, while initial COD concentration (600 mgL−1), ad-
sorbent dose (4 g per 100 mL), pH (8) and at room temperature were
kept constant. Increasing the contact time increased the uptake of the
organic matter on the surface of the adsorbent. This is might be hap-
pened due to the reason that the adsorbate can get sufficient time to
interact with the surface of adsorbent which increases the chance of
attachment. This indicates that equilibrium was not yet achieved.
Hence, the longer time needed to achieve the equilibrium might be
attributed to the fact that the concentration of the initial solution is so
high.
Additionally, pseudo-first-order and pseudo-second order were
employed to determine adsorption kinetics phenomena which indicated
in Eq. (2) [37]. The pseudo-first-order equation was given as follows:
k1 t
log(qe − qt ) = log qe −
2.303 (2)
where the parameters qt and qe are the amount of organic matter ad-
sorbed onto activated carbon of BFA (mg g−1) at time t and equili-
brium, respectively. The adsorption rate constant (k1 = 0.008 min−1)
was observed whereas the calculated adsorptive capacity (qe) was
76 mg g−1 (R2 = 0.88).
Also a pseudo second order rate equation was employed to evaluate
the adsorption process. The pseudo second order rate equation is given
by:
t 1 t
= +
qt k2 qe 2 qe (3)
−1 −1
where k2 (g mg min ) is the rate constant of a pseudo second order
adsorption model. The plot of t vs t is shown in Fig. 2 below. The
qt
J. Fito et al.
estimated values of the pseudo second order rate constant (k2) and the
adsorption capacity were 0.0002 g mg−1 min−1 and
116.3 mg g−1(R2 = 0.98), respectively.
To select the best model for adsorption kinetics, the R2 value and
calculated value of adsorption capacity (qecal) of the pseudo-first-order
and pseudo-second order were compared. The experimental value of
maximum adsorptive capacity (qeexp) was determined to be
124.80 mg g−1. This clearly showed that the second order model is
performing better as the R2 is very high and qecal is nearly the same as
the experimental value (qeexp).
3.7. The effect of temperature on adsorption
The effect of temperature on adsorption efficiency was highly pro-
nounced and presented in Fig. 3. This is clearly shown that adsorption
process was endothermic. Increasing adsorption efficiency with tem-
perature is attributed to the increasing diffusion rate of organic mole-
cules which will create many contact opportunities with a number of
active sites on the surface the adsorbent. Hence, increasing mobility of
the adsorbate at high temperature can result in increasing the uptake of
organic matter on BFA. Raising adsorptive capacity of the adsorbent
with temperature might be associated with an increasing kinetic energy
of the adsorbate which enhances its availability at the active sites of the
adsorbent [38]. The uptake of the organic matter on BFA was increased
from 29.5 to 75.5% as temperature raised from 15 to 55 °C. Ad-
ditionally, increasing adsorption with temperature indicated the che-
misorption nature of the adsorption phenomena [39] which is con-
sistent with the results of this study. Even though increasing
temperature favors the adsorption process of this study, sometimes
adsorptive capacity can be decreased with increasing temperature. At
elevated temperatures, the earlier adsorbed molecules on a surface of
adsorbent tend to desorb because the adsorptive forces between the
active sites of adsorbent and adsorbate species are weakened.
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Journal of Environmental Chemical Engineering 5 (2017) 5381–5388
Fig. 2. The rate of pseudo-second-order adsorption against time.
3.8. Adsorption thermodynamics
The study of adsorption thermodynamics phenomena was carried
out over the range of temperatures 15 to 55 °C. At each equilibrium
point of adsorption processes, the equilibrium adsorption distribution
constant sometimes also called equilibrium constant (Kd) can be de-
termined in three ways. The first two ways were based on Freundlich
and Langmuir constants. The third method was based on adsorption
thermodynamics equilibrium. For this study, the third method was
employed to determine Kd values as shown in Eq. (4).
qe
Kd =
ce (4)
where ce is the equilibrium concentration of solution (mgL−1), qe
(mg g−1) is the amount of organic matters adsorbed on the surface of
the adsorbent (BFA) and Kd is the adsorption equilibrium constant. The
Kd value of this experiment was calculated at the adsorption equili-
brium of different temperatures (15, 25, 35, 45 and 55 °C).
To determine the correct value of the thermodynamic parameters,
this Kd was calculated to become dimensionless by multiplying 1000
which is almost the same as the density of solution (ρ ≈ 1000 gL−1)
[40]. This density concept was used in [41] in order to calculate the Kd
value which was missed in many literature and sources of errors in
determining the values of other thermodynamic parameters. The value
of the Gibbs free energy change during the adsorption process is related
to the equilibrium constant (Kd) by Equation (5). The equilibrium
constant Kd increased with increasing temperature from 15 to 55 °C
which indicated that the adsorption of organic matters favored at
higher temperature 55 °C.
ΔG = −RTlnK d (5)
The errors aroused when the values of ΔG is calculated using Eq. (5)
was adjusted since Kd is multiplied by correction factor and become
dimensionless parameter otherwise the values of Gibbs free energy
Fig. 3. Removal efficiency of COD against temperature.
J. Fito et al.
were incorrect. Thermodynamic analysis showed that all values of
Gibbs free energy change were ranged from −5.61 to
−11.84 kJ mol−1 which showed that high driving force is required for
adsorption process. These negative values were confirmed that the
adsorption of organic matter onto BFA adsorbent was spontaneous and
thermodynamically favored. However, The positive values of Gibbs free
energy change indicated the small amount of energy is needed from
external to carry out adsorption which declared the increases of free
energy change with temperature [42]. Hence, it can be concluded the
increase in non-spontaneity nature is in parallel with the increase of
adsorption temperature under this specific condition. The degree of
negativity for ΔG increases with increasing temperature which con-
firmed that the degree of spontaneity and feasibility of the adsorption
process are increased with increasing temperature. This process might
be associated with the increase in the mobility of the adsorbate parti-
cles.
Change in enthalpy and entropy were calculated according to the
Van’t Hoff equation (Eq. (6)). Moreover, the Van’t Hoff concept can give
some information on the sorption mechanism for studied adsorbent
which shows the relationship between the adsorption coefficient Kd and
other thermodynamic parameters at different temperature that ex-
pressed as Equation (6).
ΔH ΔS
ln K d = − +
RT R (6)
where the ΔH is the enthalpy change (kJ mol−1), ΔS is the entropy
change (kJ mol−1 K−1), R is universal gas constant
(8.314 J mol−1 K−1) and T is the absolute temperature (K).
The equilibrium distribution coefficient was associated with tem-
perature in linear plot of lnKd versus 1 which was shown in Fig. 4. From
T
this linear relationship, the values of enthalpy and entropy changes
were determined from the slope and intercept of the equation, respec-
tively. The Coefficient of determination (R2) of the equation was 0.98.
Overall the adsorption thermodynamics analyses help to predict the
nature of adsorption phenomena. The calculated values of enthalpy and
entropy change with the Gibbs free energy change were shown in
Table 4. From the adsorption process, the values of the enthalpy change
were positive (42.29 kJmol−1) which confirmed that the process was
endothermic and increased the removal of organic pollutants on the
surface of the BFA with increasing temperature. The idea of physi-
sorption or chemisorption process can be identified according to the
magnitude of ΔH. Endothermic nature of adsorption system most likely
indicates physical adsorption since adsorption increases with increasing
the temperature of the system. Even though the level of the interactions
between adsorbate and adsorbent was determined by physisorption or
chemisorption, sometime adsorption increases with increasing tem-
perature which might be indicative of chemisorption and vice versa for
physisorption. For those change in enthalpy values greater than
20 kJ mol−1, the process is predominantly governed by chemical in-
teractions, chemisorption [43]. The value of ΔH assigned to judge
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Journal of Environmental Chemical Engineering 5 (2017) 5381–5388
Table 4
Adsorption thermodynamic results of organic matters on BFA.
SN Temperature (K) ΔG (kJ Kd ΔH(kJ ΔS(kJ
(mol)−1) (mol)−1) (Kmol)−1)
1 288 −5.61 10.4 42.29 0.17
2 298 −6.98 16.7
3 308 −8.97 33.2
4 318 −11.06 65.6
5 328 −11.84 76.9
whether the physisorption or chemisorption is a controversy in litera-
ture but the magnitude of the ΔH that lie in the range of 2.1 to 20.9 and
80 to 200 kJ mol−1 are considered as physical and chemical adsorption,
respectively [44].
Another thermodynamics parameter is the entropy change which
normally shows whether the adsorption mechanism is an associative or
dissociative based on its magnitude and sign. Usually, the negative
value of entropy change involves association mechanism. The value of
the entropy change in this study was 0.17 kJ (Kmol) −1 and positive.
The positive value of the entropy change involves the dissociation
process which indicates some structural changes in the adsorbates and
adsorbents in the process [42]. On the other hand, the positive entropy
change also indicated that there was a good affinity between the ad-
sorbate and adsorbent [45]. Generally, thermodynamics study showed
that the adsorption process was a feasible, spontaneously, endothermic
and physicochemisorption process.
4. Conclusions
Investigation of physicochemical properties of distillery spent wash
showed that high amount of organic matter which expressed in terms of
COD and BOD; and total solids were obtained with high acidic property.
Moreover, the ratio of BOD/COD of distillery spent wash was very low
(0.03) which indicated that treatment of the spent wash by biological
method would be a big challenge and need to look for another treat-
ment option like adsorption. Adsorptive capacity of activated carbon
produced from bagasse fly ash was increased with increasing contact
time, initial COD concentration and temperature. The adsorptive ca-
pacity (qe) was also increased from 6 to 92.4 mg g−1 as the initial COD
concentration was increased from 1000 mgL−1 and 6000 mgL−1. The
uptake of the organic matter on the adsorbent surface was increased
from 29.5 to 75.5% with the temperature (from 15 to 55 °C).
Adsorption kinetics study follows pseudo-second order model with
k2 = 0.0002 g mg−1 min−1. The qe value was in good agreement with
the observation data. Based on adsorption thermodynamic, the change
in Gibbs free energy showed that the adsorption process was feasible
and spontaneous whereas the enthalpy change was positive which re-
vealed that the process is endothermic. The positive value in entropy
change confirmed that the increasing of randomness at the solid-liquid
Fig. 4. The thermodynamics analysis plotting curve of lnKd versus 1/T.
J. Fito et al.
interface. Finally, activated BFA is the promising option for removal of
organic matter removal (COD) from molasses spent wash under the
study condition.
Funding sources
This work was supported by United States Agency for International
Development (USAID) under the USAID/HED funded grant in the
Africa-US Higher Education Initiative − HED 052-9740-ETH-11-01.
Acknowledgments
We would like to thank Ethiopian Institute of Water Resources,
Addis Ababa University for supervising financial support given by the
United States Agency for International Development (USAID) under the
USAID/HED funded grant in the Africa-US Higher Education Initiative
− HED 052-9740-ETH-11-01. We would also like to thank Ghent
University, Faculty of Bioscience Engineering for offering us complete
laboratory facilities and Ethiopian Sugar Corporation Research and
Development Center for providing us bagasse fly ash and all other ne-
cessary supports.
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